Use of zinc sulfide as an anti-mite agent

ABSTRACT

The invention relates to a novel use of zinc sulphide as agent for combating acarids. The invention also relates to compositions with acarid-combating properties comprising zinc sulphide as additive, in particular polymer compositions, and to yarns, fibres, filaments and articles obtained from these compositions; it is also targeted at liquid or solid compositions for cleaning and/or treating textile surfaces, in particular carpets, including fitted carpets.

The invention relates to a novel use of zinc sulphide as agent forcombating acarids. The invention also relates to compositions withacarid-combating properties comprising zinc sulphide as additive, inparticular polymeric compositions, and to yarns, fibres, filaments andarticles obtained from these compositions; it is also targeted at liquidor solid compositions for cleaning and/or treating textile surfaces, inparticular carpets, including fitted carpets.

Acarids are harmful not only to agriculture, gardens or forestry butalso to man. They can result in particular in allergies, asthma,rhinitis or conjunctivitis in the latter. In the human habitat, forexample, acarids are present in a not insignificant amount, inparticular in carpets, including fitted carpets, furniture, surfacecoverings, sofas, curtains, bedding, or mattresses and pillows. Attemptsare therefore being made in numerous applications, such as the textilefield, to limit the spread of acarids in textile surfaces, for examplewith the purpose of preventing ailments in man due to acarids. In themedical sectors, it is also of great importance to limit the spread ofacarids on operating equipment, building materials or clothes.

Organic insecticidal and acaricidal compositions are known, inparticular in the field of agriculture. Such compositions are, forexample, disclosed in Patent FR 2 710 239. These compositions can beapplied by spraying, by vaporization, by dusting, by spreading ofgranules and by fumigation, directly or using equipment, over harmfulinsects and acarids or over the sites where the harmful insects andacarids are present.

Other agents which exhibit biocidal properties have been known for avery long time and used, for example, for cosmetic applications or forfungicidal applications. Among these agents, components based on metals,such as silver, copper or zinc, are those well known.

Numerous finishes comprising bioactive compounds have been developed inorder to confer biocidal properties on textile surfaces. However, thesefinishes always have a limited strength and their effects disappearafter one or more washings. It is therefore in numerous cases moreadvantageous to introduce the active principle directly into the articlewhich has to exhibit a bioactive property.

To this end, it is known to introduce a bioactive agent into yarns spunin solution or spun by coagulation. The bioactive agent is thenintroduced into the solvent of the polymer.

Commercial organic agents for combating acarids are also known. Mentionmay be made, for example, of benzylbenzoate, permethrin or3-iodo-2-propynyl butylcarbamate, sold by Troy under the referenceKertex 100. However, these agents cannot be introduced intothermoplastic polymers since they do not withstand the temperatures forforming the latter or can be converted at these temperatures.

Other bioactive agents which can be incorporated in thermoplasticpolymers have been developed. Patent Application WO 01/11956 discloses,for example, the use of a complex formed from dendritic polymer and frombiocidal compound based on at least one biocidal metal or metal ion.This complex can be introduced into the molten thermoplastic polymer.

For the polymers formed in the molten phase, the introduction is knownof inorganic fillers supporting an element based on a bioactive metal.These fillers can be introduced during the polymerization process orduring the forming process. A great many solutions have been providedfor the preparation of inorganic fillers. These fillers have to exhibita satisfactory dispersibility in the polymer and an acceptable colourand they must not have an excessively detrimental effect on theproperties of the polymers. Mention may be made as example of inorganicfiller for combating acarids of a glass filled with boric acid sold byIshisuka Glass under the reference Segurocera.

There is a constant search for novel charges for combating acarids whichare inexpensive and easy to employ in polymeric compositions, inparticular.

Thus, zinc sulphide, an inorganic filler known as such, for example asmatifying agent for textile yarns obtained by spinning polymericcompositions, also exhibits properties for combating acarids and theirdesired properties with regard to cost, ease of use and introductioninto polymeric matrices: this is because it easily disperses in thesematrices and it withstands their forming temperatures and is not alteredat these temperatures.

A first subject-matter of the present invention is therefore the noveluse of zinc sulphide as agent for combating acarids.

In a second subject-matter, the invention also relates to compositionswith acarid-combating properties comprising zinc sulphide and asadditive, for example liquid or solid compositions for cleaning and/ortreating textile surfaces (carpets including fitted carpets, inparticular) or polymeric compositions.

Finally, in a third subject-matter, the invention relates to yarns,fibres, filaments and articles obtained from the compositions describedabove. These yarns, fibres, filaments and articles exhibit very goodpermanent acarid-combating properties.

The zinc sulphide of the invention can be provided in various forms: itcan, for example, be a zinc sulphide particle or a partial or completecoating of zinc sulphide on a particle which is different in nature,such as an inorganic particle of silica or of titanium dioxide, and thelike. The zinc sulphide, when it is in the form of an essentiallyspherical particle, can have a small diameter, of the order of 0.3 μm,which allows it to be used in textile yarns, fibres or filaments, inparticular. The size of the particles of zinc sulphide according of theinvention is not limited and can range up to several millimetres. Thezinc sulphide can also be provided in the form of platelets.

Acarids belong to the group of arthropods divided into subclasses:insects and arachnids. Acarids are arachnids and are often parasites andpathogens. There are a large number, several tens of thousands, of knownacarids, a very limited number of which are harmful to man. Acarids havea size of 200 to 500 microns and are virtually invisible to the eye.They live essentially in a moist atmosphere (65 to 80% relativehumidity) under dark conditions and at ideal mean temperatures of 15 to25° C. Their life span is ±3 months.

Mention may be made, as species of acarids, of, for example, the speciesof the genera Acarus, Tyrophagus and others. The speciesDermatophagoides is present in particular in house dust and thus relatesmore particularly to harmful effects on man. Two varieties ofDermatophagoides are encountered D. pteronyssinus and D. farinae.Acarids of the species Dermatophagoides feed mainly on human skin scalesand on waste from the nails or hair, including body hair, on remnants offood, and the like. The present invention is concerned more particularlywith the species of the Dermatophagoides.

According to the first subject-matter of the invention, the zincsulphide can be introduced into any environment comprising acarids inorder to reduce or eliminate the amount of acarids present in theenvironment. The term “environment” is understood to mean any mediumcomprising at least acarids. The environment can be a gas, preferablyair.

The term “to reduce” is understood to mean to decrease the amount ofacarids present in the environment, compared with the amount present inthe environment before the introduction into the environment of the zincsulphide. The term “to reduce” is also understood to mean to reduce therate of growth of new acarids over time and in the environment. The term“to reduce” is also understood to mean to reduce the rate ofreproduction of the acarids. The term “to eliminate” is understood tomean to eliminate from the environment most of the acarids, that is tosay to kill the acarids present in the environment (acaricide) or torender them inactive. The term “to eliminate” is also understood to meanto prevent the growth of new acarids.

The zinc sulphide of the first subject-matter of the invention can beused as it is, that is to say alone, but it is preferably supported byvarious inactive supports in the liquid, solid or gas form. Furthermore,additives, such as a surfactant, a dispersant, an adhesive, a stabilizeror propellants, can be added, if necessary, to prepare formulations,such as powders for dusting, granules, emulsions, solutions in an oil,wettable powders, sols, flowing compositions, aerosols, coating agents,fumigants, fuming agents and ULV formulations (formulations for agentsat an ultimate low volume).

The amount of zinc sulphide of the first subject-matter of the inventionapplied can vary with the formulation form and with the time and thedate, the site and the method of application, the nature of the harmfulorganisms and the degree of injury.

The application of the zinc sulphide of the first subject-matter of theinvention can be carried out, for example, by spraying, by vaporization,by dusting, by spreading granules and by fumigation, directly or usingequipment, over harmful acarids or over the sites where harmful acaridsare spreading.

The zinc sulphide of the invention, as agent for combating acarids, canalso be employed in any composition and in particular in any compositionor product used in the field of textile yarns, fibres, filaments andarticles. It can in particular be employed in polymeric compositions andin cleaning and/or treating compositions for textile surfaces, inparticular carpets, including fitted carpets.

Thus, the second subject-matter of the invention relates to compositionswith acarid-combating properties comprising zinc sulphide as additiveand in particular to polymeric compositions, as well as to cleaningand/or treating compositions for textile surfaces, in particularcarpets, including fitted carpets.

The zinc sulphide as agent for combating acarids can be used asadditive, for example in formulations for the sizing of yarns, fibresand filaments, in finish or paint formulations applied to textilesurfaces, in detergent formulations, such as washing compositions fortextile surfaces (in particular for carpets, including fitted carpets),in adhesives used, for example, for the manufacture of fitted carpets orcoverings, in backings for textile surfaces, and the like.

According to a specific embodiment of the second subject-matter of theinvention, the proportion by weight of zinc sulphide with respect to thetotal weight of the composition is less than or equal to 5%.

According to a first preferred embodiment of the second subject-matterof the invention, the composition is a liquid or solid composition forcleaning and/or treating textile surfaces, in particular carpets,including fitted carpets.

The said compositions can comprise from 0.05 to 5% of their dry weightof zinc sulphide.

When they are liquid compositions, they additionally comprise water andoptionally at least one organic solvent. The amount of water canrepresent at least 10%, preferably at least 50%, of the weight of thecomposition; this amount of water can range up to 98% of the weight ofthe composition.

Mention may be made, among the organic solvents, of aliphatic oraromatic alcohols or glycol ethers (methanol, ethanol, propanol,isopropanol, propanediol, ethylene glycol, glycerol, benzyl alcohol,butoxy propoxy propanol, and the like), as well as “degreasing”solvents, such as terpenes. These solvents can represent from 0.1 to 50%of the weight of the liquid composition.

The liquid compositions can additionally comprise other conventionaladditives employed in liquid cleaning compositions for textile surfaces,in particular carpets, including fitted carpets.

Mention may in particular be made of:

-   -   anionic surface-active agents (alkyl ester sulphonates, alkyl        sulphates, alkylamide sulphates, salts of saturated or        unsaturated fatty acids, and the like), nonionic surface-active        agents (polyalkoxylated derivatives of alkylphenols, of fatty        acids, of amines, of fatty acid amides or of amidoamines,        condensates of ethylene oxide or propylene oxide with        ethylenediamine, alkylpolyglucosides, and the like), amphoteric        surface-active agents (alkyl amphoacetates, and the like) or        zwitterionic surface-active agents (betaines); they can        represent from 1 to 20%, preferably from 5 to 15%, of the weight        of the liquid composition;    -   inorganic builders (polyphosphates, silicates, carbonates,        zeolites, and the like) or organic chelating or sequestering        builders (water-soluble polyphosphonates, carboxylic polymers or        copolymers or their water-soluble salts, polycarboxylic acids or        their water-soluble salts, salts of polyacetic acids, and the        like); it can represent from 5 to 80% of the weight of the        liquid composition;    -   soil-release agents (cellulose derivatives, polyester copolymers        based on ethylene terephthalate and polyoxyethylene        terephthalate units, sulphated polyester oligomers or        copolymers, and the like); they can represent from 0.01 to 10%,        preferably from 0.1 to 5%, of the weight of the liquid        composition;    -   bleaching agents (hydrogen peroxide);    -   agents for inhibiting colour transfer (polyamines N-oxide, or        copolymers of N-vinylpyrrolidone and of N-vinylimidazole);    -   foam suppressants;    -   propellants (isobutane, propane, and the like);    -   and other additives, such as enzymes, buffers, fillers,        fragrances, and the like.

When they are solid compositions for cleaning and/or treating textilesurfaces, they additionally comprise at least one filler which canrepresent from 40 to 98.5% of the weight of the solid composition.

These fillers are in particular of borax type, preferably sodium boratedecahydrates, in particular sodium tetraborate decahydrate; they canalso be inorganic salts, such as sulphates, chlorides, carbonates,bicarbonates, phosphates or nitrates, or sodium in particular, aluminiumsalts, such as sodium aluminate, and sodium citrate.

The solid compositions can additionally comprise other conventionaladditives employed in solid cleaning compositions for textile surfaces,in particular carpets, including fitted carpets.

Mention may in particular be made of:

-   -   adsorbents, such as cellulose powders, polyurethane foams or        bentonite;    -   alcohol ethers, such as ethylene glycol monomethyl ether,        diethylene glycol monomethyl ether, propylene glycol monomethyl        ether, dipropylene glycol monomethyl ether, ethylene glycol        monoethyl ether, diethylene glycol monoethyl ether or ethylene        glycol monobutyl ether;    -   anionic, nonionic, cationic or amphoteric surface-active agents        in the liquid or solid form, such as those described above;    -   antistatic agents, such as aluminium oxides, quaternary ammonium        salts, ethoxylated alcohols, alkylphenols, ethoxylated amines,        anionic soaps, sulphates or sulphonates;    -   agglomerating agents.

The compositions for cleaning and/or treating textile surfaces can bedeposited on the surface to be treated by different methods:

-   -   machine with a high steam throughput: expulsion of hot steam        under high pressure, spraying over the fitted carpet and then        vacuum suction.    -   direct impregnation of the cleaning formulation over the surface        to be treated, with optional rubbing using a sponge or a brush.        The product can subsequently be removed by absorption on an        absorbent or by vacuum suction.    -   spraying of the cleaning formulation over the fitted carpet in        the form of fine drops. The product can optionally be dried by        passing hot air, the solids deposited subsequently being removed        by suction or brushing.    -   application using a carpet shampooer.

The liquid compositions can optionally be diluted with water before use.

The compositions for cleaning and/or treating textile articles can beemployed in amounts, expressed on a dry basis, of 0.01 to 200 mg/m² ofsurface area to be treated.

According to a second preferred embodiment of the second subject-matterof the invention, the composition is a polymeric composition.

The polymeric composition of the invention comprises a polymeric matrix.Any polymeric matrix known to a person skilled in the art can beemployed in the context of the present invention.

The polymeric matrix of the invention is preferably a thermoplasticmatrix. The thermoplastic matrix in accordance with the invention is athermoplastic polymer.

Mention is made, as examples of polymers which may be suitable, of:polylactones, such as poly(pivalolactone), poly(caprolactone) andpolymers of the same family; polyurethanes obtained by reaction betweendiisocyanates, such as 1,5-naphthalene diisocyanate, p-phenylenediisocyanate, m-phenylene diisocyanate, 2,4-toluene diisocyanate,4,4′-diphenyl-methane diisocyanate, 3,3′-dimethyl-4,4′-diphenyl-methanediisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate,4,4′-diphenylisopropylidene diisocyanate, 3,3′-dimethyl-4,4′-diphenyldiisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate,3,3′-dimethoxy-4,4′-biphenyl diisocyanate, dianisidine diisocyanate,toluidine diisocyanate, hexamethylene diisocyanate,4,4′-diisocyanatodiphenylmethane and compounds of the same family, anddiols with long linear chains, such as poly(tetramethylene adipate),poly(ethylene adipate), poly(1,4-butylene adipate), poly(ethylenesuccinate), poly(2,3-butylene succinate), polyether diols and compoundsof the same family; polycarbonates, such aspoly[methanebis(4-phenyl)-carbonate],poly[1,1-etherbis(4-phenyl)carbonate],poly[diphenylmethanebis(4-phenyl)carbonate],poly[1,1-cyclohexanebis(4-phenyl)carbonate] and polymers of the samefamily; polysulphones; polyethers; polyketones; polyamides, such aspoly(4-aminobutyric acid), poly(hexamethylene adipamide),poly(6-aminohexanoic acid), poly(m-xylylene adipamide), poly(p-xylylenesebacamide), poly(2,2,2-trimethylhexamethylene terephthalamide),poly(meta-phenylene isophthalamide), poly(p-phenylene terephthalamide)and polymers of the same family; polyesters, such as poly(ethyleneazelate), poly(ethylene 1,5-naphthalate),poly(1,4-cyclohexanedimethylene terephthalate), poly(ethyleneoxybenzoate), poly([lacuna]para-hydroxybenzoate),poly(1,4-cyclohexylidenedimethylene terephthalate), polyethyleneterephthalate, polybutylene terephthalate and polymers of the samefamily; poly(arylene oxides), such as poly(2,6-di-methyl-1,4-phenyleneoxide), poly(2,6-diphenyl-1,4-phenylene oxide) and polymers of the samefamily; poly(arylene sulphides), such as poly(phenylene sulphide) andpolymers of the same family; polyetherimides; vinyl polymers and theircopolymers, such as polyvinyl acetate, polyvinyl alcohol, polyvinylchloride, polyvinylbutyral, polyvinylidene chloride, ethylene-vinylacetate copolymers and polymers of the same family; acrylic polymers,polyacrylates and their copolymers, such as polyethyl acrylate,poly(n-butyl acrylate), polymethyl methacrylate, polyethyl methacrylate,poly(n-butyl methacrylate), poly(n-propyl methacrylate), polyacrylamide,polyacrylonitrile, poly(acrylic acid), ethylene-acrylic acid copolymers,ethylene-vinyl alcohol copolymers, acrylonitrile copolymers, methylmethacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers,methacrylate-butadiene-styrene copolymers, ABS and polymers of the samefamily; polyolefins, such as low density poly(ethylene),poly(propylene), low density chlorinated poly(ethylene),poly(4-methyl-1-pentene), poly(ethylene), poly(styrene) and polymers ofthe same family; ionomers; poly(epichlorohydrins); poly(urethane)s, suchas polymerization products of diols, such as glycerol,trimethylolpropane, 1,2,6-hexanetriol, sorbitol, pentaerythritol,polyetherpolyols, polyesterpolyols and compounds of the same family,with polyisocyanates, such as 2,4-tolylene diisocyanate, 2,6-tolylenediisocyanate, 4,4′-di-phenylmethane diisocyanate, 1,6-hexamethylenediisocyanate, 4,4′-dicyclohexylmethane diisocyanate and compounds of thesame family; polysulphones, such as the products of reaction between asodium salt of 2,2-bis(4-hydroxyphenyl)propane and4,4′-dichloro-diphenyl sulphone; furan resins, such as poly(furan);cellulose ester plastics, such as cellulose acetate, cellulose acetatebutyrate, cellulose propionate and polymers of the same family;silicones, such as poly(dimethylsiloxane),poly(dimethylsiloxane-co-phenylmethylsiloxane) and polymers of the samefamily; or blends of at least two of the above polymers.

According to a specific alternative form of the invention, thethermoplastic matrix is a polymer comprising star-shaped or H-shapedmacromolecular chains and, if appropriate, linear macromolecular chains.The polymers comprising such star-shaped or H-shaped macromolecularchains are disclosed, for example, in the documents FR 2 743 077, FR 2779 730, U.S. Pat. No. 5,959,069, EP 0 632 703, EP 0 682 057 and EP 0832 149.

According to another specific alternative form of the invention, thethermoplastic matrix of the invention is a polymer of random tree type,preferably a copolyamide exhibiting a random tree structure. Thesecopolyamides with a random tree structure and their process ofpreparation are disclosed in particular in the document WO 99/03909.

The thermoplastic matrix of the invention can also be a compositioncomprising a linear thermoplastic polymer and a star-shaped, H-shapedand/or random tree thermoplastic polymer as are described above.

The compositions of the invention can also comprise a hyperbranchedcopolyamide of the type of those disclosed in the document WO 00/68298.

The compositions of the invention can also comprise any combination ofstar-shaped, H-shaped or random tree thermoplastic polymer orhyperbranched copolyamide described above.

Mention may be made, as other type of polymeric matrix which can beemployed in the context of the invention of thermally stable polymers:these polymers are preferably infusible or exhibit a softening point ofgreater than 180° C., preferably ≧200° C., or greater. These thermallystable polymers can, for example, be chosen from aromatic polyamides,polyamideimides, such as polytrimellamideimides, or polyimides, such asthe polyimides obtained according to the document EP 0 119 185, knowncommercially under the P84 trade name. The aromatic polyamides can be asdisclosed in Patent EP 0 360 707. They can be obtained according to theprocess disclosed in Patent EP 0 360 707.

Mention may also be made, as other polymeric matrix, of viscose,cellulose, cellulose acetate, and the like.

The polymeric matrix of the invention can also be of the type of thepolymers used in adhesives, such as vinylacetate copolymer plastisols,acrylic latices, urethane latices, PVC plastisols, and the like.

Preference is very particularly given, among these polymeric matrices,to semicrystalline polyamides, such as polyamide 6, polyamide 6,6,polyamide 11, polyamide 12, polyamide 4, polyamides 4,6, 6,10, 6,12,6,36 or 12,12, or semiaromatic polyamides obtained from terephthalicand/or isophthalic acid, such as the polyamide sold under the trade nameAmodel; polyesters, such as PET, PBT or PTT; polyolefins, such aspolypropylene or polyethylene; aromatic polyamides, polyamideimides orpolyimides; the latices, such as acrylic and urethane latices; PVC,viscose, cellulose or cellulose acetate; or their copolymers and alloys.

The compositions can comprise any other additive which can be used, forexample reinforcing fillers, flame-retardants, UV stabilizers, heatstabilizers or matifying agents, such as titanium dioxide.

The third subject-matter of the invention relates to the yarns, fibres,filaments and articles obtained from the compositions and in particularthe polymeric compositions described above.

This is because the compositions, in particular polymeric compositions,according to the invention can be formed into yarns, fibres andfilaments by spinning. They can also be formed into moulded forms, forexample by injection moulding or by extrusion.

The yarns, fibres and filaments of the invention can be obtained, forexample, by melt spinning or by wet spinning the compositions, inparticular polymeric compositions, of the invention.

The polymeric compositions are preferably prepared by introducing thezinc sulphide into the molten polymer in a blending device, for exampleupstream of a spinning device. They can also be prepared by introducingthe zinc sulphide into a polymer solution, for example upstream of adevice for wet spinning. They can also be prepared by introducing thezinc sulphide into the reaction medium comprising the monomers fromwhich the polymer is formed (polymerization medium).

By spinning the compositions, in particular polymeric compositions, ofthe invention, it is possible to obtain, for example, continuousmultifilament yarns, short or long fibres, monofilaments, spun yarns forfibres, laps, slivers, tows, and the like. The product obtained can alsobe bulk continuous filaments (BCF), used in particular for themanufacture of textile coverings, such as carpets, including fittedcarpets.

All the conventional treatments in the textile field can be applied tothe yarns, fibres and filaments of the invention, such as drawing,texturing, dyeing, and the like.

In the field of textile yarns, fibres or filaments, the small size ofthe zinc sulphide particles, the diameter of which can be of the orderof 0.3 μm, is an advantage in spinning processes in particular.

The yarns, fibres and filaments described above exhibit permanentacarid-combating properties.

The invention also relates to articles obtained from the yarns, fibresor filaments described above. Such articles can be obtained inparticular from a single type of yarn, fibre or filament or, in contrastfrom a mixture of yarns, fibres or filaments of different types. Thearticle comprises at least in part yarns, fibres or filaments accordingto the invention. For a given type of yarn, fibre or filament, forexample yarns, fibres or filaments not comprising zinc sulphide, yarns,fibres or filaments of different natures can be used in the article ofthe invention.

Mention may be made, as articles, for example, of woven, nonwoven orknitted articles.

The present invention also relates to composite textile articles, thatis to say textile articles comprising several components. Thesecomponents can be, for example, short fibres, backings, adhesives,articles obtained from yarns, fibres or filaments, such as nonwovenarticles, and the like.

Mention may be made, as composite textile articles of, for example,flocked surfaces, the main components of which are generally shortfibres, an adhesive, and a backing.

Mention may also be made of tufted surfaces, used in particular infitted carpets, coverings for furniture or walls, and the like, the maincomponents of which are generally yarns, fibres, filaments or articlesobtained from yarns, fibres or filaments, a backing and optionally anadhesive.

In the context of the invention, at least one of the components of thecomposite textile article comprises zinc sulphide.

In a flocked surface, for example, the zinc sulphide can be present inthe fibres of the flocked surface and/or in the adhesive used for theflocking and/or in the backing of the flocked surface.

The fibres of a flocked surface can, for example, be fibres according tothe invention. The adhesive or the glue of a flocked or tufted surfacecan be obtained from a composition according to the invention. Thebacking of a flocked or tufted surface can also be obtained from acomposition or an article according to the invention.

The textile articles described above exhibit permanent acarid-combatingproperties.

The compositions, yarns, fibres, filaments, articles and compositetextile articles can be employed in the manufacture of any productlikely to be in contact with acarids, such as carpets, including fittedcarpets, furniture coverings, surface coverings. sofas, curtains,bedding, mattresses and pillows, and the like.

The compositions, yarns, fibres, filaments, articles and compositetextile articles of the invention preferably make possible a regulationof the population of the acarids CP, as defined in Example 12, 13 or 14,after 6 weeks at least equal to 50, the CP being measured according tothe AFNOR standard NF G 39-011. The measuring method used is one of themethods described in Example 12, 13 or 14, the method being definedaccording to the nature of the type of product to be tested(composition, powder, knitted fabric, fitted carpet, and the like).

Other details and advantages of the invention will become more clearlyapparent in the light of the examples below, given solely by way ofindication.

EXAMPLES Example 1-7 Preparation of Polyamide 6,6, Polyamide 6,Polypropylene or Polyester Powder Samples, to Which ZnS May or May notHave Been Added

PA 6,6 Matrix

The polyamide 6,6, recorded as PA 6,6, employed is a polyamide 6,6 whichdoes not comprise titanium dioxide and which has a relative viscosity of2.5 (measured at a concentration of 10 g/l in 96% sulphuric acid).

Two types of ZnS were used:

-   -   ZnS 1: ZnS with a particle size centred around 0.3 μm and        exhibiting a purity of 98%.    -   ZnS 2: ZnS with a particle size centred around 2.6 μm and        exhibiting a purity of 99.99%, sold by Aldrich under the        reference 24462-7.

The incorporation of the ZnS in the PA 6,6 is carried out by blendingpowders. The blend is dried at 80° C. for 16 h under a vacuum ofapproximately 50 mbar and is then introduced into an extrusion devicewhich provides melt blending. The operating characteristics of theextruder are as follows:

-   -   Temperature of the melt: approximately 285° C.    -   Residence time in the melt: 3 minutes

The lace obtained at the outlet of the extrusion device is quenched inwater at approximately 20° C. and then crushed and milled, after coolingwith dry ice, with a Retsch ZM 1000 ultracentrifugal mill. The particlesize of the powder obtained is less than 500 μm.

The following compositions were prepared.

The level of ZnS is expressed as weight of ZnS with respect to the totalweight of the composition. Reference Level of ZnS 1 (% w/w) Level of ZnS2 (% w/w) 1-a1 0 0 1-b1 0.5 0 1-c1 1 0 1-a2 0 0 1-b2 0 0.5 1-c2 0 1PA 6 Matrix

Two types of polyamide 6, recorded as PA 6, were used:

-   -   PA 6-1: PA 6 which does not comprise titanium dioxide and which        has a relative viscosity of 2.5 (measured at a concentration of        10 g/l in 96% sulphuric acid).    -   PA 6-2: Polyamide 6 which comprises 0.3% of TiO₂ and which has a        relative viscosity of 2.7 (measured at a concentration of 10 g/l        in 96% sulphuric acid).

The ZnS used is ZnS 1.

The incorporation of the ZnS in these PA 6 types is carried out in thesame way as in Example 1.

The operating characteristics of the extruder are as follows:

-   -   Temperature of the melt: approximately 240° C.    -   Residence time in the melt: 3 minutes

The lace obtained at the outlet of the extrusion device is quenched inwater at approximately 20° C. and then crushed and milled, after coolingwith dry ice, with a Retsch ZM 1000 ultracentrifugal mill. The particlesize of the powder obtained is less than 500 μm.

The following compositions were prepared.

The level of ZnS is expressed as weight of ZnS with respect to the totalweight of the composition. Reference PA 6 matrix Level of ZnS (% w/w)2-a PA 6-1 0 2-b PA 6-1 0.5 2-c PA 6-1 1 3-a PA 6-2 0 3-b PA 6-2 0.5 3-cPA 6-2 1

Blends were also prepared using PA 6-1, 0.5% by weight of ZnS 1 and agiven percentage of conventional pigments and stabilizer.

The stabilizer used is incorporated in the form of a PA 6 masterbatchcomprising 10% by weight of blend of KI and CuI.

The various pigments used are also incorporated in the form of amasterbatch, the characteristics of which are as follows:

-   -   Black pigment: PA 6 masterbatch comprising 20% of pigment (ref.        Sandofil MP-HPLA-AN FG from Clariant)    -   Purple pigment 1: PA 6 masterbatch comprising 25% of pigment        (ref. Sandofil MP-BPL FG from Clariant)    -   Brown pigment: PA 6 masterbatch comprising 50% of pigment (ref.        Sandofil MP-2GL-AN FG from Clariant)    -   Yellow pigment: PA 6 masterbatch comprising 25% of pigment (ref.        Sandofil MP-2G AN FG from Clariant)    -   Blue pigment: PA 6 masterbatch comprising 20% of pigment (ref.        Sandofil MP-2GLS AN FG from Clariant)    -   Red pigment: PA 6 masterbatch comprising 25% of pigment (ref.        Sandofil MP-G-AN FG from Clariant)

The incorporation of the ZnS, the stabilizer and the pigments in the PA6 is carried out by blending powders, in the same way as in Example 1,and the blend is extruded with the same operating conditions as inExamples 2 and 3, with PA 6 as matrix.

The following compositions were prepared (PA 6-1 base+0.5% ZnS 1)Pigment masterbatch Level of Level of ZnS stabilizer pigment levelmasterbatch Nature of masterbatch Reference (% w/w) (% w/w) the pigment(% w/w) 4-a1 0 0 — 0 4-a2 0.5 0 — 0 4-b1 0 0.2 black pigment 1.6 4-b20.5 0.2 black pigment 1.6 4-c1 0 0.2 purple pigment 1 1.5 4-c2 0.5 0.2purple pigment 1 1.5 4-d1 0 0.2 brown pigment 2.0 4-d2 0.5 0.2 brownpigment 2.0 4-e1 0 0.2 yellow pigment 6.0 4-e2 0.5 0.2 yellow pigment6.0 4-f1 0 0.2 blue pigment 2.3 4-f2 0.5 0.2 blue pigment 2.3 4-g1 0 0.2red pigment 3.5 4-g2 0.5 0.2 red pigment 3.5Polypropylene Matrix

The polypropylene, recorded as PP, employed is the reference Pro-Fax6301, sold by Basell. The ZnS used is ZnS 1.

The incorporation of the ZnS in the PP is carried out in the same way asin Example 1 but the blend is not dried before extrusion but is simplystored in a dessicator under P₂O₅. The operating characteristics of theextruder are specified below:

-   -   Temperature of the melt: approximately 210° C.    -   Residence time in the melt: 3 minutes

For the milling stage, the blend is cooled with dry ice and liquidnitrogen.

The following compositions were prepared.

The level of ZnS is expressed as weight of ZnS with respect to the totalweight of the composition. Reference Level of ZnS (% w/w) 5-a 0 5-b 0.55-c 1Polyester Matrix

Two polyester matrices, recorded as PET, were employed:

-   -   PET 1: PET which does not comprise titanium dioxide and which        has a viscosity index of 83.6 (measured at a concentration of 5        g/l in a 50/50 w/w mixture of phenol and dichlorobenzene).    -   PET 2: PET which comprises 0.4% of titanium dioxide and which        has a viscosity index of 74.6 (measured at a concentration of 5        g/l in a 50/50 w/w mixture of phenol and dichlorobenzene).

The ZnS used is ZnS 1.

The incorporation of the ZnS in the PET is carried out in the same wayas in Example 1 but the blend is dried at 150° C. for 16 h under avacuum of approximately 50 mbar. The operating characteristics of theextruder are specified below:

-   -   Temperature of the melt: approximately 280° C.    -   Residence time in the melt: 3 minutes

The following compositions were prepared.

The level of ZnS is expressed as weight of ZnS with respect to the totalweight of the composition. Reference PET matrix Level of ZnS (% w/w) 6-aPET 1 0 6-b PET 1 0.5 6-c PET 1 1 7-a PET 2 0 7-b PET 2 0.5 7-c PET 2 1

Example 8 Preparation of Yarns Formed from Polyamide 6,6, to Which ZnSMay or May Not Have Been Added, and Preparation of Knitted Surfaces

Preparation of the Yarns

The polyamide 6,6 employed is a polyamide 6,6 which not does notcomprise titanium dioxide and which has a relative viscosity of 2.5(measured at a concentration of 10 g/l in 96% sulphuric acid). The ZnSused is ZnS 1. The incorporation of the ZnS in the PA 6,6 is carried outby blending powders and then in the molten phase using an extrusiondevice. The melt blend is subsequently spun with a spinneret headtemperature of approximately 285° C., cooled with air (20° C., 66%relative humidity) and forwarded with a velocity at the first forwardingpoint of 4 200 m/min, so as to obtain a continuous multifilament yarn of42 dtex per 10 filaments. The multifilament or yarn is composed of 10strands and the diameter of the strand is approximately 20 μm.

The following compositions were prepared.

The level of ZnS is expressed as weight of ZnS with respect to the totalweight of the composition. Reference Level of ZnS (% w/w) 8-a 0 8-b 18-c 2Characterization of the Samples

The properties of the strands obtained are specified below:

-   -   Elongation at break: 80 to 85% (according to the standard ISO        2062)    -   Fracture toughness: 22 to 24 cN/tex (according to the standard        ISO 2062)        Preparation of the Knitted Fabrics

The preparation of the knitted surfaces is carried out by single-feederknitting. Socks with a diameter of approximately 8 cm having a weightper unit of surface area of approximately 35 g/m² are obtained. Thenumbering of the raw knitted fabrics is identical to that of the yarns:from 8-a to 8-c.

Example 9 Preparation of Yarns Made of Polyamide 6,6, to Which ZnS Mayor May Not Have Been Added, and Preparation of Knitted Surfaces

Preparation of Yarns

The polyamide 6,6 employed is a polyamide 6,6 which not does notcomprise titanium dioxide and which has a relative viscosity of 2.6(measured at a concentration of 10 g/l in 96% sulphuric acid). The ZnSis introduced in the form of a masterbatch. The masterbatch is composedof ZnS 1 introduced at 40% by weight into PA 6 with a relative viscosityof 2 (measured at a concentration of 10 g/l in 96% sulphuric acid).

It is introduced into the PA 6,6 in an extruder using a gravimetricmetering device. The melt blend is subsequently spun with a spinnerethead temperature of approximately 286° C., cooled with water andforwarded with a velocity at the first forwarding point of 600 m/min,then drawn with a draw ratio of approximately 2.7, so as to obtain acontinuous multifilament yarn of 1250 dtex per 68 filaments. Themultifilament or yarn is composed of 68 strands and the diameter of thestrand is approximately 43 μm.

The following compositions were prepared.

The level of ZnS is expressed as weight of ZnS with respect to the totalweight of the composition. Reference Level of ZnS (% w/w) 9-a 0 9-b 0.29-c 1

By way of comparison, a yarn of 1250 dtex per 68 filaments comprising0.3% of TiO₂ was added to the series; it will be numbered 9-e.

Characterization of the Samples

The properties of the yarns obtained are specified below:

-   -   Elongation at break: 40 to 44% (according to the standard ISO        2062)    -   Fracture toughness: 20 to 21 cN/tex (according to the standard        ISO 2062)        Preparation of the Knitted Fabrics

The preparation of the knitted surfaces is carried out by single-feederknitting. Socks with a diameter of approximately 6 cm with a weight perunit of surface area of approximately 300 g/m² are obtained. Thenumbering of the raw knitted fabrics is identical to that of the yarns:from 9-a to 9-c.

-   -   The knitted fabrics were subsequently dyed in softened water at        pH 6 with a bath ratio of 1/50, according to a method known to a        person skilled in the art.

Two different dyes were used:

-   -   Dye 1: acid dye Acid Blue 80®, sold by CIBA.    -   Dye 2: metal dye Acid Blue 284®, sold by Yorkshire.

No significant difference in dye uptake was observed between the 5knitted fabrics.

The samples are then numbered as indicated in the table below.

The level of ZnS is expressed as weight of ZnS with respect to the totalweight of the composition. Level of Zns Level of TiO₂ Reference (% w/w)(% w/w) Dye 9-a1 0 0 dye 1 9-b1 0.2 0 dye 1 9-c1 1 0 dye 1 9-d1 0 0.3dye 1 9-a2 0 0 dye 2 9-b2 0.2 0 dye 2 9-c2 1 0 dye 2 9-d2 0 0.3 dye 2

Example 10 Preparation of Fitted Carpets With the Yarns ObtainedAccording to Example 9

Preparation of the Yarns for the Tufting

The yarns obtained according to Example 9 were prepared according to thefollowing process: gathering together two 1250/68 yarns by twisting at220 revolutions/m and heatsetting according to the superba process knownto a person skilled in the art.

The following yarns were produced: Reference of the Reference of thethermoset yarn for the 1250/68 yarn tufting 9-a 10-a 9-b 10-b 9-c 10-c9-d 10-dPreparation of the Fitted Carpets

The yarns obtained above were tufted onto a primary backing composed ofa cloth formed from woven PP ribbons (reference: Ribbon 9020FS®, sold byCarpet Backing, Italy). A saxony velvet tuft was produced. The gauge is{fraction (1/10)}″, with 50 stitches per 10 cm, a carpet height ofapproximately 6 mm and a weight of 820 g of yarns per m².

The tufts obtained above were sometimes dyed according to the followingprocess: 30 min at 98° C., pH 6, with a dye formula composed ofmonosodium phosphate, Univadine, Tectilon yellow, Tectilon red andTectilon blue, and then softened (20 minutes at 40° C., a solution ofSandotex CD paste, 0.5%, and a tartaric acid, 0.2 g/l). These raw ordyed tufts were adhesively bonded to a secondary backing composed of aPP cloth (reference 72/730 HF®, sold by Carpet Backing, Italy). Theadhesive used is composed of SBS synthetic latices +500 parts by weightof calcium carbonate (reference of the adhesive: Latex VM 612 IM 1201Polyfass®, sold by Synthomer). It is applied to the primary backing soas to obtain 950 g of adhesive per m² of tuft approximately afterdrying.

The fitted carpets obtained are as follows: Reference of the yarnReference of the for the tufting Dyeing stage fitted carpet 10-a no10-a1 yes 10-a2 10-b no 10-b1 yes 10-b2 10-c no 10-c1 yes 10-c2 10-d no10-d1 yes 10-d2

The fitted carpets are subsequently subjected to washing extraction withwater before the activity test.

Example 11 Preparation of the Samples of Adhesive for a Fitted Carpet,to Which Samples ZnS May or May Not Have Been Added

The adhesive used is composed of SBS synthetic latices +500 parts byweight of calcium carbonate (reference of adhesive: Latex VM 612®, soldby Synthomer). The ZnS used is ZnS 1; it is introduced into the adhesivein the powder form and then blended with a mixer (Kika Labortechnik) forapproximately 5 to 10 min. The adhesive thus obtained is spread over apiece of cardboard in the form of a disc with a diameter of 8 cm and athickness of 2 to 3 mm.

The following compositions were produced.

The level of ZnS is expressed as weight of ZnS with respect to the totalweight of the composition. Reference of the adhesive Level of ZnS (%w/w) 11-a 0 11-b 5

Example 12 Characterization of the Behaviour with Respect to the Acaridsof the Samples of Pure Powders Formed from ZnS or of Powders ObtainedAccording to Examples 1-7

Principle

This characterization is carried out by a laboratory registered by theFrench Ministry of Agriculture, Fisheries and Food. The object is toevaluate the effectiveness of PA powders, to which ZnS may or may nothave been added, on the regulation of the change in a population of dustmites (dermatophagoides pteronyssinus). Monitoring is carried out overtwo development cycles of the acarids, i.e. 6 weeks.

Breeding Source of the Acarids

The acarids used originate from a laboratory strain raised on asubstrate composed of a 50/50 (w/w) mixture of wheatgerm and of brewersyeast as specks graded by sieving (fragments of less than 1 mm). Thetemperature is between 23 and 25° C. and the relative humidity ismaintained at 75% by the presence of a saturated ammonium sulphatesolution. The screen is kept in darkness.

The screen is supplied by the Laboratoire des Insectes et Acariens desDenrées [Laboratory of the Insects and Acarids of Foodstuff] of theInstitut National de Recherches Agronomiques (INRA) [National Instituteof Agronomic Research] at Bordeaux, according to the AFNOR standard NF G39-011.

Experimental Method

The method is derived directly from the AFNOR standard NF G 39-011, withthe following variations:

-   -   the experimental unit is composed of a chamber with a diameter        of 8 cm which is escapeproof with regard to acarids but which        allows ventilation and in which are found:    -   5 g of nutrient medium (food 1/NF G 39-011 appendix)    -   5 g of test powder, carpeting the bottom of the chamber    -   the study is carried out by placing 50 acarids in these devices    -   4 repetitions are carried out on the same day per experimental        factor, including for the control batches composed of the same        device but without the addition of the powder. The result is        expressed in the form of a mean and standard deviation with        regard to these 4 samples.

The monitoring consists in counting the number of living acarids afterthe time period of 6 weeks. As direct counting is rendered impossible bythe structure of the substrate, extraction by heat according to therecommendations of the AFNOR standard NF G 39-011 is used.

The criterion of effectiveness of an additive is then defined as thecoefficient of regulation of the population of acarids (CP), i.e.:${CP} = {\frac{\begin{matrix}\left( {{{Population}\quad{on}\quad{the}\quad{powder}\quad{without}\quad{the}\quad{additive}} -} \right. \\\left. {{population}\quad{on}\quad{the}\quad{powder}\quad{with}\quad{the}\quad{additive}} \right)\end{matrix}}{{Population}\quad{on}\quad{the}\quad{powder}\quad{without}\quad{the}\quad{additive}} \times 100}$

The population counts are all carried out at 6 weeks.

The CP interpretation is as follows:

-   -   the closer CP is to 0, the less effective the addition, since        the population on the sample with the additive will increase at        the same rate as that on the sample without the additive;    -   the closer CP is to 100, the more effective the addition in        having eradicated the population of acarids and having checked        its process of expansion.        Experimental Results

The data for the various experimental series are summarized in thefollowing tables:

Pure Powders for ZnS

Pure powders were tested:

-   -   ZnS 1 powder    -   ZnS 2 powder

In this case, the growth control for the acarids is nonextruded PA 6,6.The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean Nonextruded PA 6,6 864 91 ZnS 1318 31 63 ZnS 2 305 30 65

The natural expansion of the acarids on the powder without the additivevalidates the tests insofar as this confirms the extremely favourableconditions to which the powders are subjected: this is because thepopulations of acarids not subjected to the additive have a growthfactor of more than 15.

In both cases, the ZnS results in regulation of the population of theacarids.

Powders Obtained According to Example 1: PA 6,6 Matrix

The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 1-a1 939 65 1-b1 84 8 91 1-c1 9217 90 1-a2 824 23 1-b2 153 19 81 1-c2 133 15 84

The control for growth of the acarids is in accordance.

The addition of ZnS to PA 6,6 checks the process of expansion of thepopulation of the acarids.

An additional test was carried out on two powders but substituting,during the acarid-combating test, the 5 g of conventional nutrientmedium by 200 mg of nutrient medium plus “natural”, composed of 50% w/wof beard hairs washed beforehand with ethanol and of 50% w/w of housedust sieved at 20 μm.

The results are as follows: Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 1-a1 1017 114 1-b1 196 16 81

The control or growth of the acarids is in accordance.

The acarid-combating activity of the ZnS introduced into the PA 6,6 isre-encountered, even in the presence of a very rich food for theacarids.

Powders Obtained According to Examples 2 to 4: PA 6 Matrix

The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 2-a 707 23 2-b 131 10 81 2-c 12411 82 3-a 820 66 3-b 266 36 68 3-c 244 27 70 4-a1 707 23 4-a2 131 10 814-b1 610 53 4-b2 200 18 67 4-c1 782 45 4-c2 205 29 74 4-d1 800 37 4-d2146 35 82 4-e1 847 41 4-e2 114 19 87 4-f1 730 80 4-f2 210 20 71 4-g1 74968 4-g2 211 25 72

The control for growth of the acarids is in accordance with regard toeach control.

The addition of ZnS to the PA 6 checks the process of expansion of thepopulation of the acarids, this being the case even in the presence ofother additives (TiO₂, stabilizer, pigments)

Powders Obtained According to Example 5: PP Matrix

The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 5-a 833 55 5-b 359 36 57 5-c 21932 74

The control for growth of the acarids is in accordance.

The addition of ZnS to the PP checks the process of expansion of thepopulation of the acarids.

Powders Obtained According to Examples 6 and 7: PET Matrix

The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 6-a 870 61 6-b 343 27 61 6-c 18618 79 7-a 870 56 7-b 217 47 75 7-c 227 36 74

The control for growth of the acarids is in accordance.

The addition of ZnS to the PET checks the process of expansion of thepopulation of the acarids.

Example 13 Characterization of the Behaviour With Respect to the Acaridsof Knitted Fabrics Obtained According to Examples 8 and 9, of FittedCarpets Obtained in Accordance with Example 10 and of Adhesives ObtainedAccording to Example 11

Experimental Method

This characterization is carried out in the same laboratory whichcarried out the tests of Example 12. The principle of thecharacterization and the source of the acarids are identical. The methodis similar, except that the experimental unit is composed of a chamberwith a diameter of 8 cm which is escapeproof with regard to the acaridsbut which allows ventilation and in which are found:

-   -   5 g of nutrient medium (food 1/NF G 39-011 appendix)    -   a piece of knitted fabric, of fitted carpet or of adhesive to be        tested carpeting the bottom of the chamber.

The method of counting the acarids and the calculation of thecoefficient of regulation of the population of acarids (CP) areidentical to Example 12. ${CP} = {\frac{\begin{matrix}\left( {{{Population}\quad{on}\quad{the}\quad{piece}\quad{without}\quad{the}\quad{additive}} -} \right. \\\left. {{population}\quad{on}\quad{the}\quad{piece}\quad{with}\quad{the}\quad{additive}} \right)\end{matrix}}{{Population}\quad{on}\quad{the}\quad{piece}\quad{without}\quad{the}\quad{additive}} \times 100}$

The population counts are all carried out at 6 weeks.

Experimental Results

The data for the various experimental series are summarized in thefollowing tables:

Knitted Fabrics Obtained According to Example 8

The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 8-a 848 50 8-b 257 24 72 8-c 17716 81

The control for growth of the acarid is in accordance with regard to thecontrol knitted fabric.

The acarid-combating activity of the ZnS is encountered after thespinning and knitting stage: the addition of ZnS to the PA 6,6 checksthe process of expansion of the population of the acarids.

Knitted Fabrics Obtained According to Example 9

The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 9-a 878 26 9-b 391 24 55 9-a1 80946 9-b1 348 34 57 9-a2 794 88 9-b2 319 25 60

The control for growth of the acarids is in accordance with regard tothe raw or dyed control knitted fabrics.

The acarid-combating activity of the ZnS is encountered after thespinning, knitting and dyeing stage: the addition of ZnS to the PA 6,6checks the process of expansion of the population of the acarids.

Fitted Carpets Obtained According to Example 10

The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 10-a1 852 27 10-b1 258 44 7010-c1 129 15 85 10-d1 800 30 7 10-a2 791 29 10-b2 275 17 65 10-c2 112 1286 10-d2 757 38 4

The control for growth of the acarids is in accordance with regard tothe raw or dyed control fitted carpets.

The acarid-combating activity of the ZnS is encountered after the stageof spinning, of constructing the fitted carpet and of dyeing: theaddition of ZnS to the PA 6,6 checks the process of expansion of thepopulation of the acarids.

An additional test was carried out on the same dyed fitted carpets butallowing a period of time for growth of the acarids of 9 weeks insteadof the 6 weeks normally used. The results are as follows. Number ofliving acarids after 9 weeks CP Reference Mean Standard deviation Mean10-a2 1180 24 10-c2 119 7 90 10-d2 1170 106 1

The control for growth of the acarids is in accordance with regard tothe dyed control fitted carpets.

The acarid-combating activity of the ZnS is found confirmed over alonger time period and even has a tendency to become more pronounced.

Adhesives Obtained According to Example 11

The results are as follows. Number of living acarids after 6 weeks CPReference Mean Standard deviation Mean 11-a 786 39 11-b 406 20 51

The control for growth of the acarids is in accordance with regard tothe control knitted fabric.

Example 14 Characterization of the Behaviour with Respect to the Acaridsof PA Fitted Carpets Surface Treated with ZnS Powder

Principle

The object of this study is to evaluate the effectiveness of a powderintended to be applied to floor coverings in a curative and/orpreventive treatment for combating populations of dust mites.

This characterization is carried out in the same laboratory whichcarried out the test of Example 12. The source of the acarids isidentical.

The test comprises two parts:

-   -   a curative test by deposition of the product on an existing        population of acarids,    -   a preventive test with deposition of acarids on surfaces of        fitted carpets treated beforehand with the product.

Monitoring is carried out over a period of at least two cycles, i.e. 6weeks, and in comparison with a population not subjected to the product.

Experimental Method

The experimental method is derived from the experimental context of theAFNOR standard NF G 39-011.

The experimental unit is composed of a chamber with a diameter of 8 cmwhich is escapeproof with regard to the acarids but which allowsventilation and in which are found:

-   -   a piece of short-pile polyamide fitted carpet as floor    -   5 g of nutrient medium (dust+skin scales)    -   the corresponding dose of the test powder.

The ZnS tested is ZnS 1.

Curative Test Procedure

-   -   approximately 50 active acarids are placed on the fitted carpets    -   the test product is mixed with the food and sprinkled with a        salt cellar over the fitted carpet containing the acarids    -   4 repetitions are carried out on the same day as experimental        factor, including for the control batches composed of the same        device but without the product    -   the product is applied at a rate of 160 mg/m²    -   2 counts of the populations of acarids are carried out after        incubating for 4 and 6 weeks under optimum development        conditions.        Preventive Test Procedure    -   the product is mixed with the food and sprinkled with a salt        cellar over pieces of acarid-free fitted carpets    -   one month later, approximately 50 active acarids are placed on        the treated fitted carpets    -   4 repetitions are carried out as experimental factor, including        for the control batches composed of the same device but without        the product (same control as for the curative test)    -   the product is applied at the rate of 10, 40, 80 and 160 mg/m²    -   counting of the population of acarids is carried out after        incubating for 6 weeks under optimum development conditions.

The monitorings consist in counting the number of living acarids afterthe time period of 4 or 6 weeks of incubation.

The method of counting the acarids and the calculation of thecoefficient of regulation of the population of acarids (CP) areidentical to Example 12. ${CP} = {\frac{\begin{matrix}\left( {{{Population}\quad{on}\quad{the}\quad{untreated}\quad{piece}} -} \right. \\\left. {{population}\quad{on}\quad{the}\quad{treated}\quad{piece}} \right)\end{matrix}}{{Population}\quad{on}\quad{the}\quad{untreated}\quad{piece}} \times 100}$

The population counts on controlled and treated are all carried out atthe same number of weeks.

Experimental Plan

Curative Test:

-   -   powder tested: 160 mg/M²    -   untreated control

Preventive Test:

-   -   powder tested: 10, 40, 80 and 160 mg/m²    -   untreated control        Experimental Results

The data for the various experimental series are summarized in thefollowing tables:

Curative Test

The results are as follows. Number of Number of living acarids CP livingacarids CP after 4 weeks 4 after 6 weeks 6 Treat- Amount Standard weeksStandard weeks ment (mg/m²) Mean deviation Mean Mean deviation MeanNothing 257 39 905 32 ZnS 1 160 148 26 42 284 26 69

The control for growth of the acarids is in accordance with regard tothe untreated fitted carpet.

The acarid-combating activity of the ZnS is found and the effectincreases with incubation time.

Preventive Test

The results are as follows. Number of Number of living acarids CP livingacarids CP after 4 weeks 4 after 6 weeks 6 Treat- Amount Standard weeksStandard weeks ment (mg/m²) Mean deviation Mean Mean deviation MeanNothing 257 39 905 32 ZnS 1 10 242 29 6 849 37 6 ZnS 1 40 154 19 40 36120 60 ZnS 1 80 142 14 45 315 33 65 ZnS 1 160 123 12 52 290 28 68

The control for growth of the acarids is in accordance with regard tothe untreated fitted carpet.

The acarid-combating activity of the ZnS is found and the effectincreases with the incubation time and the concentration deposited onthe fitted carpet.

Example 15 Liquid Composition with Acarid-Combating Properties forTextile Surfaces

Ingredients Function % by mass Water 90.5%  ZnS   1% Acrylic polymer0.2% 2-Amino-2-methyl-1-propanol 0.2% 7 EO ethoxylated C₁₂-C₁₄ alcoholNonionic 0.1% surfactant Isoparaffin hydrocarbon Solvent   8%

Example 16 Liquid Composition with Acarid-Combating Properties forTextile Surfaces

Ingredients Function % by mass Water 75.5%   ZnS 2% Sodium lauryl ethersulphate Anionic 10%  surfactant Disodium lauramide Anionic 10% sulphosuccinate surfactant Isopropanol Solvent 2% EDTA(ethylenediaminetetraacetic Sequestering 0.5%   acid) agent

Example 17 Liquid Stain-Removing Composition with Acarid-CombatingProperties for Textile Surfaces

Ingredients Function % by mass Water 93.72%  ZnS 0.08%  Tripropyleneglycol methyl ether Hydrophobia   5% solvent 2.6 EO ethoxylated C₁₀-C₁₂alcohol Nonionic 0.5% surfactant Sodium lauryl sulphate Anionic 0.3%surfactant EDTA Sequestering 0.4% agent

Example 18 Pulverulent Composition with Acarid-Combating Properties forCleaning Fitted Carpets

Ingredients Function % by mass Sodium borate decahydrate 79%  ZnS 1%Aluminium oxide 12%  Ethylene glycol monoethyl ether 6% Linear alcoholpolyethylene Nonionic 1% glycol surfactant Fragrance 0.5%   Anticakingagent 0.5%  

Example 19 Aerosol Composition with Acarid-Combating Properties forCleaning Fitted Carpets

Ingredients Function % by mass Sodium lauryl sulphate Foaming 2.5%surfactant ZnS   1% Sodium lauryl sarcosinate Anionic 3.5% surfactantDipropylene glycol n-propyl ether Solvent   3% Polyethylene glycolmonooleate 0.3% Isobutane Propellant 4.25%  Propane Propellant 0.75% Fragrance 0.5% Sodium tetraborate Oxidizing 0.75%  agent Water 83.45% 

1-21. (canceled)
 22. A process for combating acarids on a textilesurface, comprising the step of applying to said surface an efficientamount combating acarids amount of zinc sulphide.
 23. A compositionhaving acarid-combating properties comprising zinc sulphide as additive.24. The composition according to claim 23, wherein the zinc sulphidepresents a proportion by weight ofs less than or equal to 5% withrespect to the total weight of the composition.
 25. The compositionaccording to claim 23, being a liquid or solid composition for cleaningand/or treating textile surfaces.
 26. The composition according to claim25, wherein the surfaces are carpets or fitted carpets.
 27. Thecomposition according to claim 25, wherein the zinc sulphide representsa proportion of at least 0.05% of the dry weight of the composition. 28.The composition according to claim 25, wherein the composition is aliquid composition comprising from 10 to 98% of its weight of water andoptionally from 0.1 to 50% of its weight of at least one organicsolvent.
 29. The composition according to claim 25, further comprisingat least one filler.
 30. The composition according to claim 29, whereinthe filler is a sodium borate decahydrate.
 31. The composition accordingto claim 30, wherein the filler represents from 40 to 98.5% of theweight of the composition.
 32. The composition according to claim 23,wherein the composition is polymeric.
 33. The composition according toclaim 32, further comprising a thermoplastic matrix.
 34. The compositionaccording to claim 33, wherein the thermoplastic matrix is athermoplastic polymer selected from the group consisting of polyamides;polyesters; polyolefins,; aromatic polyamides; polyamideimides;polyimides; latices,; PVC; PET; PBT; PTT; viscose; cellulose; andcellulose acetate.
 35. The composition according to claim 34, whereinthe thermoplastic polymer is polyamide 6, polyamide 6,6, polyamide 11,polyamide 12, polyamide 4, polyamide 4,6, polyamide 6,10, polyamide6,12, polyamide 6,36, polyamide 12,12, polypropylene, polyethylene,acrylic lattices, or urethane latices
 36. Yarns, fibres or filamentsmade by the process of spinning a polymeric composition as defined inclaim
 32. 37. Article formed from a polymeric composition as defined inclaim
 32. 38. Article obtained from yarns, fibres or filaments asdefined in claim
 36. 39. A composite textile article withacarid-combating properties, wherein at least one of the components ofthe article comprises zinc sulphide.
 40. The textile article accordingto claim 39, comprising, as components, at least one backing and yarns,fibres or filaments.
 41. The textile article according to claim 41,further comprising an adhesive.
 42. The textile article according toclaim 40, wherein the yarns, fibres or filaments comprise zinc sulphide.43. The textile article according to claim 40, wherein the backingcomprises zinc sulphide.
 44. The textile article according to claim 41,wherein the adhesive comprises zinc sulphide.
 45. The textile articleaccording to claim 39, having a flocked surface or a tufted surface.